Redox-Metered Paired Electrolysis: A Strategy for Comprehensive Deaminative C(sp3)–C(sp2) Cross-Coupling
- 1Department of Chemistry
- 2California
Abstract
Interfacing transition metal catalysts with radical intermediates is a powerful paradigm for organic synthesis; however, it often requires the precise synchronization of independent catalytic cycles, and this requirement can limit scope and generality. We report a novel electrochemical strategy, which we term “redox-metered paired electrolysis,” in which the formation of a radical precursor in situ gates the rate of activation of its intended partner, thus promoting efficient cross-coupling across diverse substrate classes. We apply this strategy to the deaminative C(sp3)–C(sp2) cross-coupling of primary alkyl amines and aryl electrophiles, facilitated by the design of a bench-stable, dihydropyridine activating group. Notably, our redox-metered approach enables the cross-coupling of four categories of amines with five classes of aryl electrophiles—triflates, chlorides, bromides, iodides, and activated carboxylic acids—all under one unified set of conditions. Nineteen total pairs of amine and aryl electrophile classes are demonstrated to undergo catalytic cross-coupling (>75 examples), including seven that have not been reported previously. These novel pairs include elusive, yet valuable bond formations, such as the deaminative cross-coupling of phenol-derived aryl triflates with amines and the coupling of aryl halides with α-amino acids. Time course analysis supports the proposed mechanism and reveals design principles for future applications of this strategy.
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BibTeX
@misc{george2026redoxmetered,
title = {{Redox-Metered Paired Electrolysis: A Strategy for Comprehensive Deaminative C(sp3)–C(sp2) Cross-Coupling}},
author = {Emma N. George and Mariah C. Castillo and Johnny Z. Wang and Chiyoung Ahn and Colin A. Gould},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008631/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008631/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Redox-Metered Paired Electrolysis: A Strategy for Comprehensive Deaminative C(sp3)–C(sp2) Cross-Coupling
AU - Emma N. George
AU - Mariah C. Castillo
AU - Johnny Z. Wang
AU - Chiyoung Ahn
AU - Colin A. Gould
PY - 2026
DA - 2026/09/10
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008631/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008631/v1
AB - Interfacing transition metal catalysts with radical intermediates is a powerful paradigm for organic synthesis; however, it often requires the precise synchronization of independent catalytic cycles, and this requirement can limit scope and generality. We report a novel electrochemical strategy, which we term “redox-metered paired electrolysis,” in which the formation of a radical precursor in situ gates the rate of activation of its intended partner, thus promoting efficient cross-coupling across diverse substrate classes. We apply this strategy to the deaminative C(sp3)–C(sp2) cross-coupling of primary alkyl amines and aryl electrophiles, facilitated by the design of a bench-stable, dihydropyridine activating group. Notably, our redox-metered approach enables the cross-coupling of four categories of amines with five classes of aryl electrophiles—triflates, chlorides, bromides, iodides, and activated carboxylic acids—all under one unified set of conditions. Nineteen total pairs of amine and aryl electrophile classes are demonstrated to undergo catalytic cross-coupling (>75 examples), including seven that have not been reported previously. These novel pairs include elusive, yet valuable bond formations, such as the deaminative cross-coupling of phenol-derived aryl triflates with amines and the coupling of aryl halides with α-amino acids. Time course analysis supports the proposed mechanism and reveals design principles for future applications of this strategy.
ER -